TY - JOUR

T1 - The Sulfolene Protecting Group

T2 - Observation of a Direct Photoinitiated Cheletropic Ring Opening

AU - Skov, Anders B.

AU - Folkmann, Linnea M.

AU - Boguslavskiy, Andrey E.

AU - Röder, Anja

AU - Lausten, Rune

AU - Stolow, Albert

AU - Johnson, Matthew S.

AU - Pittelkow, Michael

AU - Nielsen, Ole John

AU - Sølling, Theis I.

AU - Hansen, Thorsten

PY - 2021

Y1 - 2021

N2 - Photolabile protecting groups offer synthetic routes with facile deprotection by photolysis, providing higher yields with less workup. Protecting groups producing only gaseous byproducts upon removal are particularly desirable as sustainable reagents. Cheletropic reactions provide just this combination of photocleavable groups with gaseous byproducts. However, only few protecting groups for cheletropic reactions have been described and little is known about their photochemistry and associated stereochemistry. Here we show that the sulfolene protecting group, used for diene protection and functionalization, can be photochemically removed. First, using TD-DFT, we conclude that the photochemical ring-opening occurs conrotatorily in a concerted process, consistent with the Woodward-Hoffmann rules. Experimentally, we demonstrate that this process can be photoinitiated by radiation between 180 and 300 nm and confirm the proposed stereochemistry in solution. Using time-resolved photoelectron spectroscopy, we determine that the first steps in the photochemical ring-opening of sulfolene occur on ultrafast timescales (≤84 fs), consistent with a fully concerted process. Our findings expand applications of the sulfolene protecting group and promise an easy strategy for control of cis-trans isomerization.

AB - Photolabile protecting groups offer synthetic routes with facile deprotection by photolysis, providing higher yields with less workup. Protecting groups producing only gaseous byproducts upon removal are particularly desirable as sustainable reagents. Cheletropic reactions provide just this combination of photocleavable groups with gaseous byproducts. However, only few protecting groups for cheletropic reactions have been described and little is known about their photochemistry and associated stereochemistry. Here we show that the sulfolene protecting group, used for diene protection and functionalization, can be photochemically removed. First, using TD-DFT, we conclude that the photochemical ring-opening occurs conrotatorily in a concerted process, consistent with the Woodward-Hoffmann rules. Experimentally, we demonstrate that this process can be photoinitiated by radiation between 180 and 300 nm and confirm the proposed stereochemistry in solution. Using time-resolved photoelectron spectroscopy, we determine that the first steps in the photochemical ring-opening of sulfolene occur on ultrafast timescales (≤84 fs), consistent with a fully concerted process. Our findings expand applications of the sulfolene protecting group and promise an easy strategy for control of cis-trans isomerization.

U2 - 10.1002/cptc.202100048

DO - 10.1002/cptc.202100048

M3 - Journal article

VL - 5

SP - 863

EP - 870

JO - ChemPhotoChem

JF - ChemPhotoChem

SN - 2367-0932

IS - 9

ER -